Synthesis of prebiotic organics from CO2 by catalysis with meteoritic and volcanic particles

The emergence of prebiotic organics was a mandatory step toward the origin of life. The significance of the exogenous delivery versus the in-situ synthesis from atmospheric gases is still under debate. We experimentally demonstrate that iron-rich meteoritic and volcanic particles activate and catalyse the fixation of CO2, yielding the key precursors of life-building blocks. This catalysis is robust and produces selectively aldehydes, alcohols, and hydrocarbons, independent of the redox state of the environment. It is facilitated by common minerals and tolerates a broad range of the early planetary conditions (150–300 °C, ≲ 10–50 bar, wet or dry climate). We find that up to 6 × 108 kg/year of prebiotic organics could have been synthesized by this planetary-scale process from the atmospheric CO2 on Hadean Earth.

period. This solution was refluxed at 53 • C for 8 h. From this point on, work was carried out under air. After cooling, the reaction batch was transferred to another vessel and toluene (300 mL) was added over a period of one hour. A tetrabutylammonium hydroxide solution (7.5 mg of a 40 % solution in 7.5 mL of methanol) was added over a period of 30 min.
Methanol and ethanol were removed under reduced pressure. After centrifugation, the supernatant was washed alternately with toluene and cyclohexane (3 x 90 mL). The solvent was removed under reduced pressure. The resulting white powder was calcined 450 • C for 12 h at and annealed at 1000 • C for 12 h.
For the reductions and reactions under high pressure, a high-pressure stainless steel autoclave with a 200 mL glass insert with digital pressure gauges, fine throttling valve, and temperature sensor 330 mm. The autoclave is tightened with silver gasket. The temperature was adjusted by a heating hood 20 S, equipped with a magnetic stirrer. The autoclaves were purchased from Carl Roth, Karlsruhe, Germany.
For reactions under aqueous conditions an addition a three-way ball valve was installed between the autoclave and the fine throttling valve. The autoclaves were pressurized with a homebuild high pressure screening setup. [3] The Planetary Ball Mill 33 Pulverisette 7 was purchased from Fritsch GmbH, Idar-Oberstein, Germany and was used with two grinding bowls of 20 mL stainless steel and 12 balls of 10 mm stainless steel.
A Thermo Trace gas chromatograph (San Jose, California, USA) equipped with a splitinjector (250 • C), a flame ionization detector (250 • C) for the quantitative analyses, and for the identification a quadrupole ion trap (PolarisQ MS) mass spectrometer or quadrupole (ISQ single quadrupole MS) mass spectrometer was used, respectively. Gas chromatography analysis was performed on a 25 m GE-SE-30 250 nm (ID 250 µm).

A. Analyses of the minerals
As support minerals four silicates (diopside, olivine, montmorillonite and silica gel) and a phosphate mineral (hydroxy apatite) were chosen, that have been already present on the Earth. The morphology and composition were analyzed by Scanning Electron Microscope (SEM) and Energy Dispersive X-ray Spectroscopy EDX. The elemental composition is summarized in Table S1. Table S1. Summarized properties and composition of the mineral supports: Name, molecular formula, category, and mass percent of oxygen (O, % atom ), magnesium (Mg, % atom ), silicon (Si, % atom ), calcium (Ca, % atom ), iron (Fe, % atom ), sodium (Na, % atom ), aluminum (Al, % atom ), and phosphorus (P, % atom ) determined by scanning electron microscopy (SEM). Various metal precursors, which have been present on the Earth, were selected catalytically active materials: iron and stone meteorites and volcanic ash. These materials are composed of consisting of iron, nickel, and other trace metals.
The composition of these materials is summarized in Table S2 and Table S3.  Table S3. Summarized composition of the volcanic ash measured by ICP: mass fraction in milligram per gram volcanic ash of iron (Fe, mg/g), nickel (Ni, mg/g), cobalt (Co, mg/g), phosphorus (P, mg/g), gallium (Ga, mg/g), germanium (Ge, mg/g), iridium (Ir, mg/g), silicon (Si, mg/g), calcium (Ca, mg/g), chrome (Cr, mg/g). copper (Cu (mg/g), potassium (K, mg/g), magnesium (Mg, mg/g), manganese (Mn, g/mg), sodium (Na, mg/g), sulfur (S, mg/g), titanium (Ti, mg/g), and zinc (Zn, mg/g). Preparation of the stock solution for the authentic meteoric and volcanic ash The meteorites and the volcanic ash were dissolved in aqueous nitric acid yielding the stock solutions. The stone meteorite and the volcanic ash are not completely dissolved under these conditions, therefore the solutions were disperged and used without filtration.

Procedure for the synthesis of the supported oxidized catalysts
For the preparation of the supported oxidized catalysts, the support (silica gel, hydroxy apatite, olivine, diopside and montmorillonite clay) was impregnated with the stock solution.
The prepared suspension was dried at 100 • C and subsequently calcined at 450 • C for 4.5 h.
Under these conditions the metal nitrates completely decompose under formation of the corresponding metal oxides.      For the reduction of the oxidized catalysts (≈1 g) of the impregnated support materials was transferred in the glass insert (quartz glass) of the autoclave. The autoclave was evacuated and flushed with nitrogen (three times). After evacuation (9 × 10 −3 mbar), hydrogen (≈ 50 bar) was pressurized into the autoclave. Reduction of the oxidized catalysts was achieved by heating to ≈ 300 • C for 17 h.

B. Reaction procedures
Prior reaction the excess hydrogen of the reduced and cooled down supported catalyst was released and carbon dioxide and, subsequently, hydrogen or water were added with a defined partial pressure or volume, respectively. The pressurized autoclave was then heated to the corresponding temperature. The detailed reaction conditions are listed in Section VII or IX. After the set reaction time, the autoclave was cooled to 0 • C (to condense the volatile compounds). In order to separate the formed organic compounds from the catalyst, a distillation was performed. The black, frozen catalyst was cooled to -180 • C and transferred to the glass distillation apparatus. This apparatus was evacuated 3 × 10 −2 mbar.
Then, the leg of the distillation apparatus with the catalyst was heated to 210 -220 • C and the evaporated compounds were condensed into a flask cooled with liquid nitrogen (-180 • C). After completion of the distillation process the apparatus was opened and after a warming the reaction products were collected by adding dichloromethane (3× overall 0.3 mL or 0.5 mL). S15

A. Blank measurements
The following blank measurements were performed to exclude contaminations of the dichlormethane, catalyst, distillation, minerals, metal sources, ball mill and autoclave system: 1. dichloromethane (the solvent used), 2. the catalyst reduced in the autoclave and then distilled (without CO 2 addition), 3. the reaction in the autoclave system without catalyst, and 4. the minerals (diopsid, hydroxy apatit, and olivine milled in the ball mill) used for the catalyst were reduced without pretreatment, as in a CO 2 fixation, and then used under standard conditions (T = 300 • C, p = 45 bar, H 2 :CO 2 = 2:1, t = 3-4) in the CO 2 fixation. The detected products are summarized in the following table (table S7)  Table S7. Blank measurement with catalysts: metal source and mineral, the conditions: reaction times (t, in d), ratio of partial pressures of hydrogen and carbon dioxide (H 2 :CO 2 ) and the overall pressure (p, in bar) and with the resulting products: Mass of oxygenated products (oxy. p., in mg), n-alkanes (n-alk, in mg), iso-alkanes (iso-alk, in mg) and the total mass of all detective products (m T otal , in mg) in mg. by comparison of the fragmentation patterns of mass spectra in the NIST Database, based on retention times and measurements of reference compounds (n-hexane, n-heptane, n-octane, n-nonane, n-decane, n-undecane, n-dodecane, n-tridecane, n-tetradecane, n-pentadecane, iso-alkanes (2-methyl pentane, 3-methyl pentane, 2-methyl hexane, 3-methyl heptane, 3methyl octane, methanol and ethanol). These reference measurements were also used for quantification. The gas chromatography-MS spectra were evaluated using XCalibur software, Thermo, San Jose, California. Exemplary chromatograms are shown in the following figures.

Quantitative gas chromatography analysis
Quantification was achieved by calibration with dilution series of n-alkanes (n-hexane, nheptane, n-octane, n-nonane, n-decane, n-undecane, n-dodecane, n-tridecane, n-tetradecane, and n-pentadecane), alcohols (methanol and ethanol) and iso-alkanes (2-methyl pentane, 3-methyl pentane, 2-methyl hexane, 3-methyl heptane, 3-methyl octane) using FID detection. Methanol and acetaldyde can not be separated under these conditions. Therefore, the methanol/acetaldehyde ratio was determined using the intensity of two fragments (m/z = 31 and m/z = 44) in mass spectra. By comparing to a reference measurement, the ratio was found to be ≈ 1%. The low share of acetaldehyde is probably a result of its very high volatility (boiling point is 20°C), which leads to loses during the work-up. Evaluation was achieved with the QuanBrowser of Xcalibur, which performs regression analyses of the standards. Examples of calibration plots (methanol, n-octane, 2-methyl octane and 3-methyl octane) are shown in the following figure S14.
S23 Figure S14. Dilution series of methanol, n-octane, and 2-methyl octane together with 3-methyl octane are plotted against the peak areas in the FID chromatogram. The linear regression analysis provide the correlation factors for quantification. R 2 represents the correlation coefficient, σ the standard deviation of the linear regression analyses.

Analyses of formaldehyde
Because formaldehyde is highly volatile compound, which is difficult to capture and quantify, we performed the following procedure. The volatiles in the gas phase of the autoclave after reaction were separated from carbon dioxide and hydrogen by passing through by a cool-   and the metal concentration. The masses of oxygenated products (oxy. p., in mg), n-alkanes (n-alk in mg), iso-alkanes (iso-alk, in mg) and the total mass of all detected products (Σ, in mg) as well as the turnover number (TON) of of oxy. products (oxy. p., in g kg×day ), n-alkanes (n-alk, in g kg×day ), iso-alkanes (iso-alk, in S27 B. Screening of the particle size To verify the size of metal source particles, catalysts were prepared from montmorillonite and silica gel, respectively, with different metal concentrations of Campo del Cielo. The smaller the metal concentration, the smaller the nanoparticles. These catalysts, were now used in CO 2 fixation under standard conditions (T = 300 • C, p = 45 bar, H 2 :CO 2 = 2:1, t = 3-4). The results are summarized in table S10. Table S10. Results of the screening of nanoparticle size catalysts using the prepared materials: supports, their metal concentration [m(metal), in %] and their resulting particle size (∅ in nm) and the masses of oxygenated products (oxy. p. in mg), n-alkanes (n-alk, in mg), iso-alkanes (iso-alk, in mg) and the total mass of all detected products (Σ, in mg) as well as the turnover number (TON) of of oxygenated products (oxy. p., in g kg×day ), n-alkanes (n-alk, in g kg×day ), iso-alkanes (iso-alk, in        For the pressure and partial pressure screening we were used various pressures (9-45 bar) and ratios of H 2 :CO 2 (1:9 to 9:1) in CO 2 fixation under conditions (T = 300 • C, t = 3-4, catalyst = synthetic Campo del Cielo@montmorillonite). The results are summarized in table S13.

S31
The results of the experiments with water instead of hydrogen are summarized in table S14. The conditions were T = 300 • C, t = 3-4, catalyst = synthetic Campo del Cielo@montmorillonite and pressure of CO 2 = 40 bar Table S14. Results of the screening of water instead of hydrogen. The masses of oxygenated products (oxy. p., in mg), n-alkanes (n-alk, in mg), and the total mass of all detected products (Σ, in mg) as well as the turnover number (TON) of of oxygenated products (oxy. p., in g kg×day ), n-alkanes (n-alk, in  In this section, we provide a ballpark estimate of how much prebiotic organics could have been produced by the proposed scenario under the conditions representing the Hadean Earth. The major hindrance and the source of considerable uncertainties in this analysis lies in the paucity of geological and fossil records from this nascent epoch [5,6]. The radiogenic dating of primitive meteorites and dynamical modeling of the early Solar System have shown that the main accretion phase for the Earth could have lasted about ∼ 10 million years (Myr), followed by intense bombardment by planetesimals, including a Moon-forming collision at ∼ 30 − 50 Myr after its formation [7][8][9].
After the Moon-forming impact, the Earth's crust has become molten, and the early S32 Earth has been covered by a global magma ocean with a dense ( 10 − 100 bar) and hot ( 1 000 K), H 2 -and silicate-rich atmosphere [8,10,11]. The rotational period of the Earth at that epoch has been only ∼ 2.2 − 4 hours [12], leading to stronger wind gradients and atmospheric dynamics than nowadays. These harsh conditions unfavorable for the origin of life should have rapidly become more clement, as detrital zircon crystals provided evidence for the existence of stable continental crust and hydrosphere on the early Earth already at ∼ 4.4 Ga, only 50 − 100 Myr after the Moon-forming impact [13,14].
At that stage, the early Earth's atmosphere has become cooler, 150 − 300 C and CO 2rich due to the H 2 thermal escape and volatile outgassing during the solidification of the magma ocean [15][16][17][18][19][20][21]. The water vapor has condensed out from the atmosphere and formed a hot pristine ocean with twice the volume of the modern hydrosphere, where the subaerial surface has likely been dominated by the volcanoes and volcanic islands [8,22,23]. The subaerial surface area has been much smaller than today, covering at most S land 0.1 − 1% of the entire Earth' surface (which corresponds to 5 × According to the lunar cratering records, the initial intense, sterilizing bombardment of the Earth at ∼ 4.5 has been followed by a steady decline in the impactor's flux, potentially with another intense, ∼ 10 − 100 Myr period of the Late Heavy Bombardment (LHB) at ∼ 3.8 − 3.9 Ga [26][27][28][29][30][31]. The exogenous delivery has likely been dominated by massive, 10 − 000 km asteroids from the inner terrestrial planet zone [32][33][34][35]. The size-number statistics for the late veneer' carriers suggests a range of possibilities, from a single delivery of the highly siderophile elements via a Pluto-sized object (with a radius of 1 000 km) to a multitude (> 10 − 100) of smaller impacts by ∼ 100 − 200 km asteroids [21]. In the single giant impact scenario, the oceans would evaporate and full reduction of all water and CO 2 would occur, leading to a H 2 -rich atmosphere and efficient in situ production of organics S33 via Fischer-Tropsch and Urey-Miller syntheses [36]. In contrast, in the scenario of multiple smaller impacts, the oceans wouldn't vaporize, and the atmosphere will remain CO 2 -rich and H 2 -poor.
Planetesimals with sizes 20 km that formed within ∼ 2.7 Myr after the formation of the Ca-Al-rich inclusions (CAIs) have become differentiated due to the radiogenic heating by the short-lived radionuclides [37]. A fraction of these differentiated planetesimals shattered by planetesimal collisions has formed a population of iron cores like 16 Psyche, as well as smaller metallic fragments and particles [38,39]. The relative abundance of these iron-rich cores could have been at least ∼ 10% of the total impactor's population [40]. Another exogenous source of metals on the early Earth has been partly differentiated stony and stony-iron planetesimals similar to the S-type main-belt asteroids. These siliceous planetesimals have contained up to ∼ 10 wt% of metallic iron [41], and had a relative abundance of 20%. The most primitive carbonaceous chondrite planetesimals, similar in composition to the C-type meteorites, had retained ∼ 1 − 15 wt% of metals and metal oxides, and hence could have been an exogenous source of both the metallic and iron-rich silicate particles [42][43][44].
We use the early bombardment model for the "late veneer" from Pearce et al. [24]. It has a linearly declining exogenous delivery rate, with a minimum and maximum values of  [24,45]. Over a timespan of 10 − 100 Myr, at least several large impacts could occur [46]. Impacts by the asteroids with diameters 100 km would not have been energetic enough (< 10 28 J) to vaporize the early Earth's pristine ocean and to erode its surface, favoring the early origin and evolution of life [31,[47][48][49][50][51].
Only nanometer and micrometer-sized metallic and iron-rich silicate particles are important for the proposed organic synthesis. We consider the following main exogenous sources of such particles: 1) (sub)micron-sized iron and iron-rich interplanetary dust particles (IDPs) landing mainly intact, 2) ablation and evaporation of the iron and stony meteorites (mm-to meter-sized), and 3) evaporative impacts of 1 − 100 km-sized planetesimals [52][53][54]. Since the exogenous delivery was dominated by large asteroids [48], the evaporative impacts have likely been the most important exogenous source of the catalytic particles.
Assuming that the fraction of the iron(-rich) IDPs has been ∼ 40% as nowadays (∼ 10% iron-rich silicates and 30% iron-sulfur-nickel) [55], the delivery rate of such catalytically S34 active IDPs could have been up to ∼ 4 × 10 9 kg yr −1 at 4.4 Ga [52]. The delivery rate of the nano-and micron-sized iron(-rich) particles produced by the ablation, evaporation or airbursts of meteorites and asteroids is harder to estimate. Ablation leads to the removal of 3 − 25% of the mass from the infalling 100 kg meteorites (with typical diameters of 20 cm), depending on their atmospheric entry velocity, angle, composition and crosssection [56]. Slow meter-sized and larger meteorites lose only 1% of the initial mass by ablation, but 60 − 99% of their mass is lost by subsequent evaporation after the impact [43,56,57]. Ab initio simulations of the evaporative impacts for larger iron cores have shown that their peak temperatures could reach 15 000 K, and up to 22 wt% of the body could be vaporized, depending on the composition and the entry angle, collision velocity, etc. [58].
An FeNi impactor with a radius of 5 km and an impact velocity of 15 km s −1 would produce about 3.5 times its mass as the vapor plume [59]. Impactors with radii > 100 km could produce a mass of the vapor plume comparable with that of the modern atmosphere [46].
In the CO 2 -rich atmosphere, post-impact gases would cool and condense out at ∼ 1 700 K as metals, metal oxides and silicates on a timescale of less than a few months [46,47,60,61].
Condensates are also launched from the impact zone to space and reenter the atmosphere all around the globe, undergoing secondary heating and ablation [59]. The iron and iron-rich condensate particles will react with atmospheric gasses, reducing atmospheric CO or CO 2 into CH 4 and other light hydrocarbons [46,60]. Experiments has shown that such "ironsilicate smokes" can catalytically convert H 2 , CO and N 2 to water, CO 2 , NH 3 , CH 4 with comparable efficiency to industrial catalysts [62]. Sekine et al. (2003) have estimated that a typical size of the condensed particles would be ∼ 10µm-1 mm and smaller [59]. In our calculations, we assumed that the fraction of catalytically active, nanometer-to micron-sized iron and iron-rich silicate particles is 0.1−1% of the evaporated mass of the impactors. We estimate that a total delivery rate of the catalytically active exogenous particles could have been up to ∼ 3×10 9 −2×10 13 kg yr −1 .
Only a fraction of catalytic particles would settle on the subaerial Earth' surface, though.
Sedimentation of these nano-and (sub-)micron-sized particles in the dynamically active atmosphere, with atmospheric circulations and winds, would result in their total delivery rate onto the subaerial surface ofṘ exo cat ∼ 5 × 10 7 − 4 × 10 11 kg yr −1 . Please bear in mind that giant impacts are stochastic and can deliver a substantial mass ( 10 10 kg) of catalytic particles within a short time period. Even in an extreme case of a single impact by a S35 planetesimal with a diameter of 100 km, a representative density of 2 700 kg m −3 , a mass of ≈ 1.4×10 18 kg, the mass of the nano/micron-sized condensates would cover only ∼ 0.1−1 cm of the Earth' surface, allowing efficient reduction of the atmospheric CO 2 and H 2 .

C. Deposition rate of volcanic ash particles
The Hadean Earth has likely been more geologically active than the Earth today due to a higher internal heat, a more radiogenic mantle, and a much higher rate of the asteroid impacts [63]. It is unclear when the plate tectonics and the modern-like volcanism at the leading to a too excessive cooling of the early Earth's atmosphere [12,78,79]. It has been estimated from geophysical models that the volcanic activity on Hadean Earth could have been at most a few times higher than nowadays [80].
With these assumptions, the emission volume of the volcanic ash into the atmosphere would be at least ∼ 20 − 100 km 3 . Volcanic ash particles with diameters 30µm would constitute a few and ≈ 30 − 50 wt% of the total ash content during basaltic and rhyolitic S36 eruptions, respectively [76]. In our calculations, the fraction of 10 wt% is assumed. The iron-rich fraction in these particles could have been up to ∼ 30 − 50%, similar to the felsic ash produced by the modern rhyolite eruptions [81,82]. We used the iron-rich fraction of 40% in our model. Hence, the total deposition rate of the catalytic iron-rich ash particles on the early Earth could have been ∼ 5 × 10 12 − 10 13 kg yr −1 .
In a ∼ 1 − 10 bar atmosphere, the volcanic ash particles with diameters 1 − 10µm brought up to the altitudes of 1 km would attain settling velocities of 0.3 − 3 m/s or higher [83]. Despite such low settling velocities, the fine ash particles often sediment very close to the volcanoes due to gravitational instabilities occurring in the interface between the ash cloud and the surrounding atmosphere [82,[84][85][86][87]. Thus, a substantial fraction (> 10%) of the catalytically active volcanic ash particles would settle on the volcanic islands, and the resulting ash deposition rate on the subaerial surface could have beenṘ vul cat ∼ 2 × 10 11 − 10 12 kg yr −1 .

D. Mass estimate of synthesized organics
The catalytically active exogenous and volcanic particles on the early Earth should have had a diversity of size distributions, depending on the distance between the impact or eruption site and the landing region, atmospheric and meteorological conditions, a type of impact or eruption, etc. [82,88]. Since only nanometer and (sub)micrometer-sized grains matter for the proposed organic synthesis, we assume that a majority of such small grains would have settled onto the subaerial surface after the sedimentation of bigger airborne fragments of a meteorite or an asteroid or volcanic pyroclasts.
The catalytic particles used in our experiments have typical sizes of ∼ 1 − 10 nm when prepared by dissolution and wet impregnation, and at least 10 µm when prepared by milling (see section IV in Supplementary Information). The measured yields of the organic synthesis for micrometer-sized catalysts are lower than those of nanoparticles by at least a factor of several (see Fig. 4 in the main text).
Then, assuming a linear relationship between the yield of the organic reactions and the reaction time, the production rate of the prebiotic organics can be roughly estimated as S37 whereṘ vul cat andṘ exo cat are the volcanic and exogenous delivery rates of the catalytic particles (kg yr −1 ), respectively, γ vul cat and γ exo cat are the yields of the organic synthesis for the volcanic and exogenous catalytic particles (in units of g of synthesized organics per kg of catalytic particles per day), respectively, and ∆t describes how long catalytic particles remain active (days).
We assume a 1 bar of the N 2 pressure and adopt the CO 2  We also assume that the minerals on the subaerial surface have resembled montmorillonite, a a typical product of the weathering of volcanic rocks at the acidic conditions representative of the early Earth [91][92][93]. The measured production yields for the volcanic and Campo del Cielo catalytic particles on the montmorillonite support have been rescaled to the assumed temperatures and pressures. Based on the results of our experiments, we assume that the catalytic particles landed on these minerals would remain active for ∼ 30 days.
Finally, using the above assumptions and values, and the delivery rate from the Eq. 1, the total production rate of the prebiotic organics by the volcanic and exogenous particles is estimated to be ∼ 10 6 − 6 × 10 8 kg yr −1 (depending on the atmospheric temperature and pressure, bombardment rate, and the volcanic activity). Thus, the total mass of the synthesized organics on Hadean Earth could have been ∼ 10 13 − 6 × 10 15 kg over a ∼ 10 Myr or ∼ 10 14 − 6 × 10 16 kg over a ∼ 100 Myr, respectively.  Figure S16. Distribution of products in the liquid phase.  Figure S17. Distribution of products in the liquid phase. Table S19. Reaction conditions and masses of the entire catalysts (Cat) and its metal share (Met).   Figure S19. Distribution of products in the liquid phase.  Figure S20. Distribution of products in the liquid phase.   Figure S22. Distribution of products in the liquid phase.  Figure S23. Distribution of products in the liquid phase.    Figure S25. Distribution of products in the liquid phase.  Figure S26. Distribution of products in the liquid phase.  Figure S27. Distribution of products in the liquid phase.

Reaction 12: Campo del Cielo @ Montmorillonite
Reaction 13: Campo del Cielo @ Montmorillonite  Figure S28. Distribution of products in the liquid phase.  Figure S29. Distribution of products in the liquid phase.     Figure S31. Distribution of products in the liquid phase.  Figure S32. Distribution of products in the liquid phase.     Figure S34. Distribution of products in the liquid phase.

Reaction 18: Campo del Cielo @ Montmorillonite
Reaction 20: Campo del Cielo @ Olivine  Figure S35. Distribution of products in the liquid phase.    Figure S37. Distribution of products in the liquid phase.  Figure S38. Distribution of products in the liquid phase.    Figure S40. Distribution of products in the liquid phase.  Figure S41. Distribution of products in the liquid phase.

Reaction 26: Muonionalusta @ Montmorillonite
Reaction 27: Campo del Cielo @ Silica Gel  Figure S42. Distribution of products in the liquid phase.  Figure S43. Distribution of products in the liquid phase.  Figure S44. Distribution of products in the liquid phase.

Reaction 29: blank @ Montmorillonite
Reaction 30: blank @ Silica Gel Table S73. Reaction conditions and masses of the entire catalysts (Cat) and its metal share (Met).      Figure S47. Distribution of products in the liquid phase.  Figure S48. Distribution of products in the liquid phase.  Figure S49. Distribution of products in the liquid phase.  Figure S50. Distribution of products in the liquid phase.

Reaction 35: Campo del Cielo @ Montmorillonite
Reaction 36: blank @ Diopside Table S85. Reaction conditions and masses of the entire catalysts (Cat) and its metal share (Met).    Reaction 38: Muonionalusta @ Diopside  Figure S53. Distribution of products in the liquid phase.

Synthesis m(Cat) [g] m(Met) [g] t [d] T [
Reaction 39: Campo del Cielo @ Hydroxyapatite  Figure S54. Distribution of products in the liquid phase.  Figure S55. Distribution of products in the liquid phase.
Reaction 41: Muonionalusta @ Hydroxyapatite  Figure S56. Distribution of products in the liquid phase.
Reaction 42: Muonionalusta @ Olivine    Figure S58. Distribution of products in the liquid phase.  Figure S59. Distribution of products in the liquid phase.

Reaction 44: Volcanic Ash @ Olivine
Reaction 45: Volcanic Ash @ Hydroxyapatite     Figure S61. Distribution of products in the liquid phase.  Figure S62. Distribution of products in the liquid phase.

Reaction 47: Volcanic Ash @ Silica Gel
Reaction 48: Campo del Cielo @ Hydroxyapatite     Figure S64. Distribution of products in the liquid phase.
Reaction 50: Gao-Guenie @ Diopside  Figure S65. Distribution of products in the liquid phase.
Reaction 51: Gao-Guenie @ Silica Gel    Figure S67. Distribution of products in the liquid phase.
Reaction 53: Volcanic Ash @ Silica Gel  Figure S68. Distribution of products in the liquid phase.
Reaction 54: Volcanic Ash @ Montmorillonite  Figure S69. Distribution of products in the liquid phase.  Figure S70. Distribution of products in the liquid phase.
Reaction 56: Volcanic Ash @ Diopside  Figure S71. Distribution of products in the liquid phase.
Reaction 57: Volcanic Ash @ Olivine  Figure S72. Distribution of products in the liquid phase.  Figure S73. Distribution of products in the liquid phase.
Reaction 59: blank @ Hydroxyapatite  Figure S74. Distribution of products in the liquid phase.
Reaction 60: Gao-Guenie @ Hydroxyapatite  Figure S75. Distribution of products in the liquid phase.  Figure S76. Distribution of products in the liquid phase.
Reaction 62: Muonionalusta @ Silica Gel  Figure S77. Distribution of products in the liquid phase.
Reaction 63: Campo del Cielo @ Montmorillonite  Figure S78. Distribution of products in the liquid phase.  Figure S79. Distribution of products in the liquid phase.
Reaction 65: blank @ blank  Figure S80. Distribution of products in the liquid phase.
Reaction 67: Campo del Cielo @ blank  Figure S81. Distribution of products in the liquid phase.  Figure S82. Distribution of products in the liquid phase.
Reaction 69: Campo del Cielo @ Diopside  Figure S83. Distribution of products in the liquid phase.
Reaction 70: Campo del Cielo @ Diopside  Figure S84. Distribution of products in the liquid phase.  Figure S85. Distribution of products in the liquid phase.
Reaction 72: Campo del Cielo @ Calcium Carbonate  Figure S86. Distribution of products in the liquid phase.
Reaction 73: Campo del Cielo @ Hydroxyapatite    Figure S88. Distribution of products in the liquid phase.  Figure S89. Distribution of products in the liquid phase.

Reaction 75: Campo del Cielo @ Montmorillonite
Reaction 76: Campo del Cielo @ Montmorillonite      Figure S92. Distribution of products in the liquid phase.